EP2382155B1 - Procédé de compression de gaz contenant du sulfure d'hydrogène - Google Patents

Procédé de compression de gaz contenant du sulfure d'hydrogène Download PDF

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EP2382155B1
EP2382155B1 EP09801448.3A EP09801448A EP2382155B1 EP 2382155 B1 EP2382155 B1 EP 2382155B1 EP 09801448 A EP09801448 A EP 09801448A EP 2382155 B1 EP2382155 B1 EP 2382155B1
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Prior art keywords
dialkyl
compressor
weight
sulfur
hydrogen
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EP2382155A1 (fr
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Andreas Wölfert
Frank Grzonkowski
Harald Jachow
Günter Renz
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/16—Hydrogen sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/16—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by oxidation of thiols, sulfides, hydropolysulfides, or polysulfides with formation of sulfo or halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds

Definitions

  • the compression of hydrogen sulfide-containing gas streams is a frequent procedural issue.
  • the use of hydrogen sulfide is often under pressure.
  • the precipitation of heavy metals from solution is carried out under pressure.
  • precipitators can be used with low volume.
  • the synthesis of alkylmercaptans by reacting hydrogen sulfide with alkanols is usually carried out by means of compressed hydrogen sulfide.
  • the alkylmercaptans may then be further reacted, e.g. to dialkyl sulfides and / or alkanesulfonic acids.
  • the hydrogen sulfide used in the above-mentioned method can be obtained, for example, from an acid gas scrubber, from refinery processes or by reacting the elements sulfur and hydrogen. Because of the toxicity of hydrogen sulfide, efforts are made to minimize both the amount of hydrogen sulfide handled in a production process and the pressure at which the hydrogen sulfide is handled. Therefore, the hydrogen sulfide is usually prepared and provided largely without pressure and compressed only in the application stage.
  • One cause of the sulfur deposits is the entrainment of elemental sulfur from the sulphurous source used, which deposits in particular on cold surfaces.
  • Another cause is the decomposition of generally contained in the hydrogen sulfide-containing source polysulfanes (H 2 S x , in particular to hydrogen sulfide and sulfur).
  • One way to increase the availability of the compressor is to purify hydrogen sulphide-containing gases prior to introduction into the compressor.
  • WO 2004/022482 the purification of hydrogen sulfide by porous media.
  • hydrogen sulfide-containing gas obtained by reacting hydrogen and liquid sulfur is passed through a filter containing a solid selected from activated carbon, alumina and silica for purification.
  • the gas thus purified is only capable to a limited extent or not at all for the separation of solid sulfur.
  • DE 102 45 164 A1 relates to a process for the conversion of polysulfanes. These polysulfanes H 2 S x are obtained in the synthesis of hydrogen sulfide by reacting hydrogen with sulfur. When the hydrogen sulfide-containing gas stream is compressed, uncontrolled decomposition of the polysulfanes into hydrogen sulfide and sulfur occurs, which leads to undesirable sulfur deposits in the entire compression region. According to DE 102 45 164 A1 For example, the polysulfanes in the hydrogen sulfide-containing gas are catalytically converted to hydrogen sulfide and sulfur by reacting hydrogen and sulfur by contacting the hydrogen sulfide-containing gas with catalytically active solids, catalytically active liquids or gases.
  • Suitable catalytically active solids are according to DE 102 45 164 A1 Activated carbon, Al 2 O 3 , SiO 2 , zeolites, glasses, oxides and mixed oxides, alkali, alkaline earth and other basic mixtures or hydroxides.
  • Suitable catalytically active liquids are basic, aqueous or alcoholic solutions of ammonia, amines or amino alcohols and solutions of alkali metal, alkaline earth metal or other basic oxides or hydroxides, sulfides or hydrogen sulfides.
  • Suitable gases are ammonia, amines or amino alcohols.
  • a disadvantage of the abovementioned processes for purifying the hydrogen sulfide obtained from the reaction of hydrogen with sulfur is the continuous consumption of the components used for the purification.
  • EP 0 850 922 A1 discloses a process for producing a compressed hydrogen sulfide-containing gas stream comprising compressing a hydrogen sulfide-containing gas stream in a compressor.
  • the object of the present invention is therefore to provide a method for the compression of hydrogen sulfide-containing gases with the highest possible availability with respect to the compressor, which requires the least possible investment.
  • compressor means not only the compressor itself but also its periphery, that is to say in particular the compressor and one or more connected heat exchangers, e.g. Tube bundle or plate heat exchanger, as well as optionally connected liquid separator.
  • the screw compressor is one of the rotary two-shaft positive displacement compressors with internal compression.
  • the screw compressor can be designed in one or two stages.
  • an injection medium can be injected during the compression.
  • the injection can be done before the first and / or second stage.
  • As the injection medium for example, water or an alcohol (for example, methanol in the production of methylmercaptan) can be used.
  • the injection medium evaporates partially or completely during the injection and compression process and thereby cools the process gas.
  • the injection medium can be condensed out or left in the process gas (an example of compression in the screw compressor with methanol as injection medium is, for example, in US Pat DE-A 196 54 515 disclosed). During the condensation of the injection medium and / or cooling, this can optionally be used again as an injection medium after filtration.
  • the liquid ring compressor used particularly preferably in the method according to the invention is a rotary positive displacement compressor of a single-shaft design.
  • water or the mixture used according to the invention for purging the compressor containing dialkyl polysulfides, dialkyl disulfides and at least one amine can be used as ring liquid in the liquid ring compressor used according to the invention.
  • water is used as ring liquid.
  • entrained ring liquid is deposited after leaving the compressor in a liquid separator (demister, separation apparatus of gas and liquid), passed through a heat exchanger for cooling and fed from there back into the compressor.
  • Suitable heat exchangers are, for example, tube bundles or plate heat exchangers.
  • the sulfur deposits occur on compression of the hydrogen sulfide-containing gas stream, in particular in the liquid ring compressor itself and in the heat exchanger (s).
  • the compaction can be carried out in step i) of the process according to the invention in one stage, two stages or several stages. Preferably, the compression takes place in one or two stages.
  • a compressor that does not have sulfur deposits generally has such a high compressor capacity that more gas is compressed than is needed for the subsequent step.
  • the excess compressed gas is being handled around the compressor from the pressure side to the suction side of the compressor (and fed back to the compressor).
  • the compressor capacity decreases with the amount of sulfur deposits in the compressor. This means that less gas is returned through the handling to the compressor. If the compressor performance is so low due to the sulfur deposits that no gas is recirculated through the handling, the compressor must be purged.
  • the inlet pressure in the compressor is generally 700 mbar to 3000 mbar absolute, preferably 1000 to 2000 mbar absolute, more preferably 1100 to 1500 mbar absolute.
  • the discharge pressure from the compressor is generally from 1000 to 7000 mbar absolute, preferably 1500 to 4000 mbar absolute, more preferably 2000 to 3200 mbar absolute, most preferably 2200 to 2800 mbar absolute, wherein the inlet pressure is less than the outlet pressure.
  • the pressure conditions in the compressor used in the method according to the invention thus differ substantially from the pressure conditions in a borehole, which usually prevail pressures of about 80 bar.
  • the inlet temperature in the compressor is generally 10 to 70 ° C, preferably 15 to 50 ° C, particularly preferably 20 to 30 ° C.
  • the outlet temperature from the compressor is generally 15 to 200 ° C, preferably 20 to 100 ° C, more preferably 25 to 50 ° C, most preferably 30 to 40 ° C. In general, the inlet temperature is lower than the outlet temperature.
  • the hydrogen sulfide-containing gas stream passed through the compressor may be prepared by any method known to those skilled in the art.
  • the gas stream can come either from sour gas scrubbing or from refinery processes or can be obtained from the elements sulfur and hydrogen.
  • the hydrogen sulfide-containing gas stream is preferably prepared from the elements sulfur and hydrogen in the presence of a catalyst or non-catalytically. Suitable processes for the preparation of the hydrogen sulfide-containing gas stream are known to the person skilled in the art.
  • DE 1 113 446 is the catalytic production of hydrogen sulfide by reacting a stoichiometric mixture of hydrogen and sulfur on a catalyst containing cobalt and molybdenum supported on a support described at temperatures below 500 ° C, preferably between 300 and 400 ° C.
  • the catalyst is in this case arranged in tubes, which are flowed through by the mixture of hydrogen and sulfur.
  • Hydrogen sulfide is produced on a molybdenum-containing catalyst of hydrogen and sulfur, wherein gaseous hydrogen is introduced into a sulfur melt containing reactor and rises through the sulfur melt in the form of gas bubbles.
  • the preparation of the hydrogen sulfide-containing gas stream is usually carried out at pressures of 0.7 to 2 bar, preferably 0.9 to 1.5 bar, most preferably 1 bar to 1.4 bar absolute.
  • the temperature of the hydrogen sulfide-containing gas stream obtained after the preparation is generally from 10 to 60.degree. C., preferably from 15 to 50.degree. C., more preferably from 20 to 45.degree. C., very particularly preferably from 25 to 40.degree.
  • H 2 S x polysulfanes
  • the polysulfanes are preferably removed before carrying out the inventive method for compressing the hydrogen sulfide-containing gas stream from the hydrogen sulfide-containing gas stream. This can be done, for example, by one of the documents mentioned above WO 2004/022482 or DE 102 45 164 A1 described method. It is also possible to purify the polysulfanes by passing them through a porous material (activated carbon filter or molecular sieves), for example as in WO 2008/087125 disclosed.
  • a porous material activated carbon filter or molecular sieves
  • a further pre-cleaning of the hydrogen sulfide-containing gas stream by desublimation in a heat exchanger preferably has a molecular sulfur content of 0.001 to 5 wt ppm, more preferably 0.005 to 2 wt ppm, most preferably 0.01 to 1 wt ppm.
  • the purity of the hydrogen sulfide used in the compression method according to the invention is generally 90 to 99.9% by volume, preferably 95 to 99.8% by volume, particularly preferably 98 to 99.7% by volume and most preferably 99 to 99.6 vol .-%.
  • dialkyl polysulfides as solvents for dissolving sulfur deposits in lines which serve to transport sulfur-containing materials, in particular deposits in the production of natural gas from sulfur-rich natural gas sources, is for the person skilled in the art, for example DE 36 10 580 A1 or US 4,248,717 known.
  • a process for dissolving sulfur by means of a liquid dialkyl polysulfide, the solvent consisting of a dimethyl polysulfide mixture, comprising 1 to 3 wt .-% dimethyl disulfide, 35 to 45 wt .-% CH 3 S x CH 3 , wherein x has a value of 3 to 5, and the remainder homologous polysulfides, wherein x has a value of 6 or more, and in particular 6 to 8 has.
  • the dialkyl polysulfide used may contain from 2 to 10% by weight of an amine, amide, mercaptan and / or mercaptide.
  • the present invention relates to a process for the compression of hydrogen sulfide-containing gases, comprising purging the compressor with a mixture containing dialkyl polysulfides, dialkyl disulfides and at least one amine, such as described in claim 1 includes.
  • the temperature and pressure conditions in lines according to DE 36 10 580 A1 prevail, as well as the hydrogen sulphide-containing gas streams used differ considerably from the conditions occurring in the compression of hydrogen sulphide-containing gases and used hydrogen sulfide-containing gas streams.
  • the devices on which the sulfur deposits are observed are also different.
  • the structural conditions in wellbores which are generally several cm diameter tubes, differ substantially from the structural characteristics of a compressor and its periphery, which generally has narrow gaps in the mm range.
  • dialkyl disulfides commonly used to remove sulfur deposits in wellbores are surprisingly unsuitable for rapidly and permanently removing sulfur deposits in a compressor, as the comparative examples in the present application show.
  • the mixture used according to the invention containing dialkyl polysulfides, dialkyl disulfides and at least one amine, despite the high viscosity, substantially better results are achieved for fast and permanent removal of sulfur deposits in a compressor.
  • Rhombic sulfur S 8 has a much higher reactivity and solubility than the so-called ⁇ -sulfur. It is known that rapid supercooling on cold surfaces, for example on heat exchanger surfaces, leads to ⁇ -sulfur.
  • the nature of the sulfur deposition and thus the solubility of the sulfur deposits depends essentially on the temperature history and the origin of the hydrogen sulfide-containing gas from which the sulfur deposits result. Experience in removing sulfur deposits from a hot well can thus not be readily transferred to the removal of sulfur deposits in a compressor. These are two completely different technical areas.
  • the rinsing of the compressor according to step ii) of the process according to the invention can be carried out continuously or discontinuously.
  • the compressor is continuously supplied with the sulfur deposits by means of the mixture according to the invention containing dialkyl polysulfides, dialkyl disulfides and at least one amine as described in claim 1.
  • the mixture used according to the invention is used e.g. when using a liquid ring compressor the ring liquid added, which is returned to the compressor.
  • a continuous implementation of the method according to the invention when using other compressors is easily possible for a person skilled in the art on the basis of his knowledge.
  • the pressure and temperature conditions in the compressor in the continuous implementation correspond to the above-mentioned pressure and temperature conditions in the compressor.
  • the compressor is briefly turned off for cleaning and treated with the aid of the mixture according to the invention containing dialkyl polysulfides, dialkyl disulfides and at least one amine as described in claim 1.
  • the temperature in the rinsing process is generally from 30 to 160.degree. C., preferably from 40 to 140.degree. C., particularly preferably from 60 to 120.degree. C., very particularly preferably from 75 to 110.degree. C. and in particular very particularly preferably from 90 to 100.degree.
  • the compressor is partially or completely filled with the mixture used for flushing.
  • the filling takes place completely.
  • the rinsing times are from 5 minutes to 1 hour, preferably from 10 minutes to 50 minutes, particularly preferably from 20 minutes to 40 minutes.
  • Suitable alkyl groups of the dialkyl disulfides and dialkyl polysulfides in each dialkyl disulfide or dialkyl polysulfide, independently of one another, are usually C 1 -C 14 -alkyl radicals, preferably C 1 -C 6 -alkyl radicals, more preferably C 1 -C 3 -alkyl radicals.
  • the alkyl radicals are methyl, ethyl, n-propyl or iso-propyl, very particularly preferably the alkyl radicals are methyl radicals.
  • the alkyl radicals may in each case be identical or different in the dialkylpolysulfides or dialkyl disulphides. Preferably they are the same.
  • the dialkylpolysulfides used in the process according to the invention are particularly preferably dimethyl polysulfides and the dialkyl disulfides are dimethyl disulfide.
  • Suitable dialkyl polysulfides have the general formula RS x -R ', where R and R' are the abovementioned alkyl radicals.
  • x denotes 3 to 12, preferably 3 to 10.
  • the dialkyl polysulfides are present in the form of mixtures of dialkyl polysulfides with different chain lengths.
  • the at least one amine present in the mixture used according to the invention for rinsing in step ii) may be a primary, secondary or tertiary aliphatic or aromatic amine.
  • the amines are primary, secondary or tertiary amines having 6 to 60 carbon atoms.
  • suitable amines are tridecylamine, fatty amines such as N, N-dimethyl-C 12 / C 14 amine and dicyclohexylamine.
  • dialkylpolysulfides dialkyl disulfides and amines are mentioned above.
  • step ii) of the densification process according to the invention is carried out continuously or batchwise, the composition of the mixture containing dialkylpolysulfides may be varied.
  • the above-mentioned mixture is particularly preferably used in discontinuous performance of step ii) of the process according to the invention.
  • the above-mentioned mixture is particularly preferably used in the continuous performance of step ii) of the process according to the invention.
  • the mixture used in step ii) contains no further components.
  • the bleaching compositions contain no surfactants.
  • the blends used to flush the compressor in step ii) are not blends that need to be specially made for flushing, but blends such as those used in processes for preparing sulfur compounds incurred according to the method of the invention compressed hydrogen sulphide gas.
  • sulfur compounds are, for example, alkyl mercaptans, dialkyl disulfides and alkanesulfonic acids.
  • the mixtures used for rinsing in step ii) of the process according to the invention are particularly preferably the amine-containing crude product from the dialkyl disulphide synthesis which can be carried out according to processes known to the person skilled in the art and is explained in more detail below.
  • the inventive method for compressing a hydrogen sulfide-containing gas stream is used in one embodiment of the present invention in combination with the preparation of sulfur compounds, in particular sulfur compounds selected from the group consisting of alkyl mercaptans, dialkyl disulfides and alkanesulfonic acids.
  • Another object of the present invention is therefore a process for the preparation of sulfur compounds selected from the group consisting of Alkylmercaptenen, dialkyl disulfides and alkanesulfonic acids comprising the reaction of a hydrogen sulfide-containing gas stream, wherein the hydrogen sulfide-containing gas stream according to the inventive method for compressing the hydrogen sulfide-containing gas stream comprising the step i) and ii) is compressed.
  • a compressed hydrogen sulfide-containing gas stream is used to produce the alkylmercaptans, wherein the compression of the hydrogen sulfide-containing gas stream used to produce the alkylmercaptans comprises steps i) and ii).
  • the alkylmercaptans are preferably prepared by reacting alkanols with a hydrogen sulfide-containing gas stream compressed in accordance with the process according to the invention comprising steps i) and ii).
  • step iii) can be carried out by customary methods known to the person skilled in the art. Suitable methods are, for example, in DE 101 37 773 A1 called. Usually, the reaction of the alkanols with the compressed hydrogen sulfide-containing gas stream takes place in the presence of catalysts.
  • Suitable catalysts are, for example, in US 2,874,129 (Metal oxides of thorium, zirconium, titanium, vanadium, tungsten, molybdenum or chromium on a porous support, for example Al 2 O 3 or pumice); EP-A 0 749 961 (Alkali carbonate on Al 2 O 3 ); EP-A 1 005 906 (Catalyst based on zirconium oxide doped with magnesium or alkaline earth metals), EP-A 0 038 540 (Zeolite catalyst with reduced amount of alkali metal cations), EP-A 0 564 706 (Catalyst of amorphous Al 2 O 3 gel or from aluminum-containing material deposited on a Al 2 O 3 gel); US 2,822,401 (activated Al 2 O 3 ), US 2,820,062 (active Al 2 O 3 with 1.5 to 15% by weight of potassium tungstate as promoter), DE 196 39 584 (active Al 2 O 3 with 15 to 40
  • catalysts based on Al 2 O 3 particularly preferably ⁇ -Al 2 O 3 , is used, which is optionally doped with promoters.
  • Suitable promoters are transition metal compounds selected from the group consisting of WO 3 , K 2 WO 4 , H 2 WO 4 , Cs 2 WO 4 , Na 2 WO 4 , MoO 3 , K 2 MoO 4 , H 2 MoO 4 , Na 2 MoO 4 , Phosphotungstate, phosphomolybdate and silicotungstate.
  • the proportion of the promoter is generally from 1 to 40 wt .-%, preferably 5 to 25 wt .-%, based on the weight of the catalyst.
  • alkylmercaptan synthesis in step iii) ⁇ -Al 2 O 3 , which is doped with K 2 WO 4 as promoter, is particularly preferably used as the catalalyzer.
  • Preferred alkylmercaptans have alkyl radicals having 1 to 14 carbon atoms, more preferably 1 to 6 carbon atoms, most preferably 1 to 3 carbon atoms, that is, methyl, ethyl, n-propyl or iso-propyl radicals.
  • alkanols ROH the corresponding alkanols are thus used in step iii) of the process for the preparation of alkyl mercaptans.
  • step iii) is carried out for the preparation of alkylmercaptans as a gas phase reaction.
  • the alkanol and the hydrogen sulfide-containing gas stream are usually heated to a temperature high enough that both the alkanol and the desired alkyl mercaptan are in the vapor phase.
  • the temperature must not be so high that a decomposition of the alkylmercaptan occurs.
  • the process according to step iii) is carried out at temperatures between 250 and 500 ° C., preferably between 300 and 450 ° C.
  • the pressure is generally 1 to 25 bar, preferably 1 to 10 bar absolute.
  • the resulting alkylmercaptans can be further reacted directly to dialkyl disulfides. Furthermore, the alkylmercaptans can be used to produce alkanesulfonic acids.
  • the "crude mercaptan stream" prepared by the above process that is, a mercaptan stream not purified by extraction or distillation, the unreacted hydrogen sulfide, water and, as minor components, dialkyl sulfide, small amounts of alkanol and Contain dialkyl ethers, continue to be used for the preparation of dialkyl disulfides.
  • the dialkyl disulfides can be prepared by any of the methods known to those skilled in the art, as far as they comprise a step for the compression of hydrogen sulfide-containing gas streams.
  • the compression of the hydrogen sulfide-containing gas streams is carried out according to the inventive method comprising the steps i) and ii).
  • step a) The preparation of the alkylmercaptans in step a) is carried out as described above with respect to the preparation of alkylmercaptans.
  • the reaction of the alkylmercaptan obtained in step a) in step b) is preferably carried out with sulfur dissolved in an organic disulfide under catalysis with an amine.
  • Suitable amines are the amines mentioned above with respect to the amines used in the mixture used for rinsing in step ii) of the process according to the invention.
  • step b) is carried out in a reaction column, with resulting low-boiling components being recycled in step a).
  • step b) of the above process is followed by the phase separation of the resulting mixture of aqueous phase which is discharged and organosulfur phase.
  • the organic disulfide used as solvent in step (b) is preferably the organic disulfide to be prepared.
  • step a) the reaction of alkanols with hydrogen sulfide on a suitable catalyst to a "crude mercaptan stream" containing mercaptan, water, hydrogen sulfide and small amounts of other by-products such as organic sulfide and ether, and in the subsequent step b ) the reaction of the "crude mercaptan stream" with sulfur dissolved in an organic disulfide under catalysis with an amine.
  • the hydrogen sulfide used in step a) is compacted according to the process comprising steps i) and ii).
  • DE 101 16 817 A1 discloses the preparation of organic disulfides in a column equipped with temperature-controllable bottoms from a crude mercaptan stream without preliminary separation by distillation.
  • the densification of the hydrogen sulfide according to the invention by a method comprising the steps i) and ii), which are mentioned above.
  • Another object of the present invention relates to a process for the preparation of alkanesulfonic acids, which is also carried out starting from compressed according to the inventive method hydrogen sulfide-containing gas streams.
  • the steps a) and b) correspond to the steps a) and b) mentioned with respect to the preparation of the dialkyl disulfides.
  • the oxidation in step c) can be achieved with various oxidizing agents.
  • the oxidizing agent hydrogen peroxide, chlorine, dimethyl sulfoxide, mixtures of dimethyl sulfoxide and hydroiodic acid and nitric acid or mixtures of said oxidizing agents can be used.
  • an electrochemical oxidation is possible. Suitable processes for the preparation of alkanesulfonic acids by oxidation of the corresponding dialkyl disulfides are known to the person skilled in the art and are described, for example, in US Pat WO 98/34914 . US 2,697,722 . US 2,727,920 and WO 00/31027 disclosed.
  • Essential in the abovementioned processes for preparing sulfur compounds selected from alkylmercaptans, dialkyl disulfides and alkanesulfonic acids is that this process comprises a step for compressing a hydrogen sulfide-containing gas stream, the compression of the hydrogen sulfide-containing gas stream being carried out according to the process of the invention comprising the steps i) and ii) becomes.
  • the present invention relates to a process for the preparation of dialkyl disulfides, in particular a process for the preparation of dialkyl disulfides, which comprises the steps (a) and (b), as listed above.
  • the compressor is preferably rinsed in the process according to the invention for the preparation of dialkyl disulfides with a mixture comprising dialkyl disulfides, dialkyl polysulfides and at least one amine as described in claim 1, this mixture being the amine-containing crude product from the dialkyl disulfide synthesis.
  • preferred compositions of the Rohaustrags are each mentioned above for a discontinuous rinsing or a continuous rinsing.
  • the mixture used for rinsing, after rinsing in step ii) of the process according to the invention, can be reintroduced into the process for the preparation of dialkyl disulphides, generally into the bottom of the dialkyl disulphide pure distillation (preferably in the discontinuous rinsing process in step ii)) or into the bottom the dialkyl disulfide reaction column after separation of the aqueous phase (preferably in the continuous rinsing process in step ii)) are recycled.
  • the characters x and xx show at which points the amine-containing crude charge for rinsing in step ii) of the compacting process according to the invention is preferably taken.
  • the point marked with x indicates the removal point from the bottom of the dialkyl disulfide pure distillation, i. the mixture which is preferably used for discontinuous purging and the point marked xx the withdrawal point from the bottom of the dialkyl disulfide reaction column after separation of the aqueous phase, i. the mixture, which is preferably used for continuous rinsing.
  • the mixture preferably used for the discontinuous rinsing in step i) of the compression method preferably corresponds to the bottoms of the dialkyl disulfide purifying distillation from the last column D of the dialkyl disulfide synthesis.
  • the mixture preferably used for continuous rinsing in step ii) of the compression method according to the invention preferably corresponds to the bottom of the column B after phase separation in the phase separator C, wherein the aqueous phase is separated and the organic phase is used for rinsing.
  • a significant advantage of the method according to the invention is that the mixture used for rinsing the compressor does not have to be complicated, but corresponds to the amine-containing crude feed from the dialkyl disulfide synthesis. This is an advantage, in particular, if the compressed hydrogen sulfide-containing gas stream is used to prepare dialkyl disulfides.
  • the hydrogen sulfide-containing gas passed through the compressor in the preparation of the abovementioned sulfur compounds generally does not correspond to the pure hydrogen sulfide-containing gas stream used at the beginning of the process but is a circulated gas which is usually 60 to 90% by weight, preferably 70 to 80% by weight .-% hydrogen sulfide, 2 to 20 wt .-%, preferably 5 to 15 wt .-% dimethyl sulfide and small amounts of carbon monoxide, methyl mercaptan and dimethyl ether.
  • a further subject of the present invention relates to the use of a mixture comprising a) from 10 to 98% by weight of dialkylpolysulfides; b) from 1.9 to 80% by weight of dialkyl disulfides and c) from 0.1 to 10% by weight of at least one amine, the total amount of dialkylpolysulfides, dialkyl disulfides and at least one amine being 100% by weight, for the removal of in the compression of sulfur-containing gas streams occurring sulfur deposits.
  • These sulfur deposits occur generally in the compressor, wherein the term compressor both the compressor itself and its periphery - as stated above - is understood.
  • Preferred mixtures used and preferably carried out compression methods are mentioned above.
  • the examples are each carried out with a liquid ring compressor with plate heat exchanger for cooling the ring liquid and handling possibility, which has sulfur deposits from carried out densification processes of H 2 S, which originates from the synthesis of the elements, and is used in a process for the synthesis of methyl mercaptan.
  • the sulfur deposits are identical in the examples and comparative examples.
  • the compressor and its periphery are turned off and filled with dimethyl disulfide, which is known to be a good solvent for sulfur. After a reaction time of 30 minutes at a temperature of 90 ° C, the compressor is free for a further operation of 3 weeks.
  • the compressor and its periphery is turned off. Instead of dimethyl disulfide, however, the compressor is filled with a polysulfide solution from the bottom of the dimethyl disulfide purifying distillation. For this purpose, the compressor and its periphery are filled with the bottom discharge. After a contact time of 30 minutes at a temperature of 90 ° C, the compressor and its periphery are free for further operation of the system for 3 months. The rinsing liquid is returned to the bottom of the di-methyl disulfide purifying distillation.
  • the organic phase from the phase separator is used after the crude dimethyl disulfide column.
  • 0.5 to 10 kg, preferably 1 to 5 kg of organic phase per 100 kg of hydrogen sulfide to be compressed are taken from the phase separator and fed into the compressor on the suction side or the ring liquid supply when using a liquid ring compressor.
  • the separated after the compressor liquid phase is preferably recycled to the bottom of the dimethyl disulfide reaction column.

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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Claims (13)

  1. Procédé pour la compression d'un flux gazeux contenant du sulfure d'hydrogène, comprenant
    (i) la compression du flux gazeux contenant du sulfure d'hydrogène dans un compresseur,
    (ii) le rinçage du compresseur avec un mélange contenant
    a) 10 à 98% en poids de polysulfures de dialkyle ;
    b) 1,9 à 80% en poids de disulfures de dialkyle et
    c) 0,1 à 10% en poids d'au moins une amine
    la somme totale de polysulfures de dialkyle, de disulfures de dialkyle et d'au moins une amine valant 100% en poids.
  2. Procédé selon la revendication 1, caractérisé en ce que le compresseur est un compresseur de gaz de recyclage, de préférence un compresseur à anneau liquide ou un compresseur à vis.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la compression dans l'étape (i) a lieu en un ou deux étages.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le rinçage dans l'étape (ii) a lieu en continu.
  5. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le rinçage dans l'étape (ii) a lieu en discontinu.
  6. Procédé selon la revendication 5, caractérisé en ce que le rinçage du compresseur dans l'étape (ii) a lieu à des températures de 30 à 160°C.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le mélange utilisé pour le rinçage dans l'étape (ii) contient
    a) 20 à 95% en poids, de manière particulièrement préférée 35 à 90% en poids, de polysulfures de dialkyle ;
    b) 4,8 à 72% en poids, de manière particulièrement préférée 9,5 à 60% en poids de disulfures de dialkyle ;
    c) 0,2 à 8% en poids, de manière particulièrement préférée 0,5 à 5% en poids d'au moins une amine ;
    la somme totale de polysulfures de dialkyle, de disulfures de dialkyle et d'au moins une amine valant 100% en poids.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le flux gazeux contenant du sulfure d'hydrogène est obtenu par préparation de sulfure d'hydrogène à partir des éléments soufre et hydrogène.
  9. Procédé pour la compression d'un flux gazeux contenant du sulfure d'hydrogène selon la revendication 1, comprenant
    (i) la compression du flux gazeux contenant du sulfure d'hydrogène dans un compresseur,
    (ii) le rinçage du compresseur avec un mélange contenant
    a) 10 à 98% en poids de polysulfures de dialkyle ;
    b) 1,9 à 80% en poids de disulfures de dialkyle et
    c) 0,1 à 10% en poids d'au moins une amine,
    la somme totale de polysulfures de dialkyle, de disulfures de dialkyle et d'au moins une amine valant 100% en poids,
    (iii) et la transformation consécutive du flux gazeux comprimé contenant du sulfure d'hydrogène en alkylmercaptans, en disulfures de dialkyle et en acides alcanesulfoniques.
  10. Procédé selon la revendication 9, caractérisé en ce que des alkylmercaptans sont préparés, comprenant la transformation d'alcanols avec le flux gazeux comprimé contenant du sulfure d'hydrogène.
  11. Procédé selon la revendication 9, caractérisé en ce que des disulfures de dialkyle sont préparés, comprenant
    a) la préparation d'alkylmercaptans par transformation d'alcanols avec le flux gazeux comprimé contenant du sulfure d'hydrogène et
    b) la transformation des alkylmercaptans obtenus dans l'étape a) par oxydation avec du soufre en disulfures de dialkyle.
  12. Procédé selon la revendication 9, caractérisé en ce que des acides alcanesulfoniques sont préparés, comprenant
    a) la préparation d'alkylmercaptans par transformation d'alcanols avec le flux gazeux comprimé contenant du sulfure d'hydrogène,
    b) la transformation des alkylmercaptans obtenus dans l'étape a) par oxydation avec du soufre en disulfures de dialkyle ; et
    c) l'oxydation des disulfures de dialkyle obtenus dans l'étape (b) avec un oxydant en acide alcanesulfonique.
  13. Utilisation d'un mélange, contenant
    a) 10 à 98% en poids de polysulfures de dialkyle ;
    b) 1,9 à 80% en poids de disulfures de dialkyle et
    c) 0,1 à 10% en poids d'au moins une amine,
    la somme totale de polysulfures de dialkyle, de disulfures de dialkyle et d'au moins une amine valant 100% en poids, pour l'élimination de dépôts de soufre qui surviennent lors de la compression de flux gazeux contenant du sulfure d'hydrogène.
EP09801448.3A 2008-12-23 2009-12-22 Procédé de compression de gaz contenant du sulfure d'hydrogène Not-in-force EP2382155B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09801448.3A EP2382155B1 (fr) 2008-12-23 2009-12-22 Procédé de compression de gaz contenant du sulfure d'hydrogène

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08172787 2008-12-23
PCT/EP2009/067739 WO2010072756A1 (fr) 2008-12-23 2009-12-22 Procédé de compression de gaz contenant du sulfure d'hydrogène
EP09801448.3A EP2382155B1 (fr) 2008-12-23 2009-12-22 Procédé de compression de gaz contenant du sulfure d'hydrogène

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EP2382155B1 true EP2382155B1 (fr) 2017-06-14

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US (1) US9067872B2 (fr)
EP (1) EP2382155B1 (fr)
JP (1) JP5675642B2 (fr)
KR (1) KR101676888B1 (fr)
CN (1) CN102264637B (fr)
BR (1) BRPI0923461A2 (fr)
CA (1) CA2747338A1 (fr)
CL (1) CL2011001560A1 (fr)
MX (1) MX2011006728A (fr)
MY (1) MY156379A (fr)
PE (1) PE20121096A1 (fr)
SG (1) SG171866A1 (fr)
WO (1) WO2010072756A1 (fr)

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CN116354858A (zh) * 2023-03-31 2023-06-30 南京科润工业介质股份有限公司 一种二烷基多硫化物的制备方法

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JP2012513367A (ja) 2012-06-14
JP5675642B2 (ja) 2015-02-25
KR101676888B1 (ko) 2016-11-16
US20110263894A1 (en) 2011-10-27
CN102264637B (zh) 2013-11-13
CL2011001560A1 (es) 2011-10-28
WO2010072756A1 (fr) 2010-07-01
PE20121096A1 (es) 2012-08-05
US9067872B2 (en) 2015-06-30
SG171866A1 (en) 2011-07-28
CA2747338A1 (fr) 2010-07-01
EP2382155A1 (fr) 2011-11-02
MX2011006728A (es) 2011-07-13
BRPI0923461A2 (pt) 2016-01-12
KR20110114550A (ko) 2011-10-19
MY156379A (en) 2016-02-15
CN102264637A (zh) 2011-11-30

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